Functionalized polymer with linking group

ABSTRACT

A functionalized polymer includes an elastomer, a terminal functional group including at least one heteroatom, and a unit intermediate the elastomer and the functional group; the intermediate unit includes a terminal moiety which, in its anionic form, is less basic than a secondary amino radical ion. Methods of making the functionalized polymer and of using it with particulate filler to make, e.g., a tire tread composition also are disclosed.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a US. national stage of international applicationPCT/US2005/038017, filed Oct. 20, 2005, and claims the benefit of U.S.provisional patent application No. 60/622,188, filed Oct. 26, 2004.

BACKGROUND INFORMATION

1. Field of the Invention

The invention relates to the manufacture and use of functionalizedpolymers capable of interacting with fillers.

2. Background of the Invention

Tire treads, power belts, and the like often are made from compositionsthat contain one or more elastomers and one or more reinforcingmaterials such as, for example, particulate carbon black and silica. Fora general discussion of this topic, see, e.g., The Vanderbilt RubberHandbook, 13th ed. (1990), pp. 603-04.

Safety and durability considerations mandate that tire treads provideboth good traction and resistance to abrasion; however, motor vehiclefuel efficiency concerns argue for a minimization in their rollingresistance, which correlates with a reduction in hysteresis and heatbuild-up during operation of the tire. The foregoing considerations are,to a great extent, competing and somewhat contradictory: a tire treadcomposition designed to improve tread traction on the road usuallyresults in increased rolling resistance and vice versa.

Typically, filler(s), elastomer(s), and additives are chosen so as toprovide an acceptable balance of these properties. Ensuring thatconstituent reinforcing filler(s) are well dispersed throughout theelastomeric material(s) in such compositions both enhancesprocessability and acts to improve physical properties such as, e.g.,compound Mooney viscosity, elastic modulus, tan δ, and the like.Resulting articles made from such compositions can exhibit desirableproperties such as reduced hysteresis, reduced rolling resistance, andgood traction on wet pavement, snow and ice.

Increasing the interaction with elastomer(s) is one way to improve theirdispersion. Examples of efforts of this type include high temperaturemixing in the presence of selectively reactive promoters, surfaceoxidation of the compounding materials, surface grafting, and chemicalmodifications to the terminal ends of the polymers with, e.g., amines,tin compounds, and the like.

Because elastomers used in such compositions often are anionicallypolymerized, attachment of certain functional groups, particularlyamines, is difficult. This is because living polymers are terminated byactive hydrogen atoms such as are present in, e.g., hydroxyl groups,thiol groups, and particularly primary and secondary amine groups. Thisundesired termination can be avoided through use of reaction schemesthat allow for attachment of non-amine N-containing compounds followedby conversion to amines, i.e., indirect attachment schemes.

Continued hysteresis reduction and provision of a direct mechanism forattaching amine functionality to a living polymer both remain highlydesirable.

SUMMARY OF THE INVENTION

In one aspect is provided a functionalized polymer that includes anelastomer with a terminal functional group including at least oneheteroatom. Between the elastomer and the functional group is a unitthat includes a terminal moiety which, in its anionic form, is lessbasic than a secondary amino radical ion.

In another aspect is provided a method of making a functionalizedpolymer. A polymer that includes at its living end a unit including aterminal moiety which, in its anionic form, is less basic than asecondary amino radical ion is allowed to react with a compound thatincludes at least one heteroatom, with the product of that reactionconstituting the functionalized polymer.

In yet another aspect is provided a composition that includes at leastone reinforcing filler and a functionalized polymer of the typedescribed above.

In a further aspect is provided a method of making a vulcanizate, suchas a tire tread, that includes vulcanizing the foregoing composition.

In a still further aspect is provided a method of directly attaching acompound that includes a primary or secondary amine group to a polymerso as to provide an amine-functionalized polymer. The method includesproviding a reaction medium in which a living polymer can be reactedwith a cyclic compound that includes a heteroatom so as to provide anextended living polymer bearing an anionic charge on the heteroatom;introducing into the reaction medium an amine that includes an activehydrogen atom attached to the amino nitrogen; and allowing the aminefunctionality to chemically bond to the extending unit so as to providean amine-functionalized polymer.

Other aspects of the present invention will be apparent to theordinarily skilled artisan from the detailed description that follows.To assist in understanding that description of the invention, certaindefinitions are provided immediately below. These definitions applyhereinthroughout unless a contrary intention is explicitly indicated:

-   -   “polymer” means the polymerization product of one or more        monomers and is inclusive of homo-, co-, ter-, tetra-polymers,        etc.;    -   “polyene” means a compound with multiple carbon-to-carbon double        bonds and includes dienes, trienes, etc.;    -   “mer” or “mer unit” means that portion of a polymer derived from        a single reactant molecule (e.g., an ethylene mer unit has the        general formula —CH₂CH₂—);    -   “homopolymer” means a polymer consisting essentially of a single        type of repeating mer unit;    -   “copolymer” means a polymer that includes mer units derived from        two reactants (normally monomers) and is inclusive of random,        block, segmented, graft, etc., copolymers;    -   “interpolymer” means a polymer that includes mer units derived        from at least two reactants (normally monomers) and is inclusive        of copolymers, terpolymers, tetrapolymers, and the like;    -   “macromolecule” means an oligomer or polymer;    -   “terminus” means an end of a constituent chain of a        macromolecule;    -   “terminal moiety” means that portion of a molecule located at        its terminus;    -   “radical” or “residue” means the portion of a molecule that        remains after reacting with another molecule;    -   “chemically bonded” means attached through a bond that is        covalent or ionic;    -   “secondary amino radical ion” means an anion having the general        formula R¹R²N⁻ where R¹ and R² independently are alkyl, aryl,        alkenyl, etc., hydrocarbon-containing chains with the proviso        that one or both of R¹ and R² can be polymeric;    -   “heteroatom” means an atom other than carbon or hydrogen; and    -   “hysteresis” means the difference between the energy applied to        deform an article made from an elastomeric compound and the        energy released as the article returns to its initial,        non-deformed state.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The functionalized polymer includes a polymeric chain with a terminalfunctional group including at least one heteroatom and, intermediate theelastomer and the functional group, a unit that includes a terminalmoiety which, in its anionic form, is less basic than a secondary aminoradical ion. This functionalized polymer can be represented by thegeneral formula E-A-G_(t) where E is an elastomer, G_(t) is a terminalfunctional group that includes at least one heteroatom, and A is a unitthat includes a terminal moiety as just described. Those of ordinaryskill in the chemical arts are familiar with relative basicities(commonly denoted as pK_(b)) and, accordingly, are aware of those atomsthat can be present in the type of terminal moiety just described. Tworelatively common heteroatoms that can form anions meeting this basicityrequirement are O and S.

The polymeric chain preferably is elastomeric. Accordingly, it caninclude mer units that include unsaturation, which can be mer unitsderived from polyenes, particularly dienes and trienes (e.g., myrcene).Preferred polyenes include C₄-C₁₂ dienes. Particularly preferred areconjugated dienes such as, but not limited to, 1,3-butadiene, isoprene,1,3-pentadiene, 2,3-dimethyl-1₅3-butadiene, and 1,3-hexadiene. Homo- andco-polymers that include just polyene-derived mer units constitute onepreferred type of elastomer.

The polymeric chain also can include mer units derived from vinylaromatics, particularly the C₈-C₂₀ vinyl aromatics such as, e.g.,styrene, α-methyl styrene, p-methyl styrene, the vinyl toluenes, and thevinyl naphthalenes. When used in conjunction with one or more polyenes,the vinyl aromatic-derived mer can constitute from about 1 to about 50%by wt., preferably from about 10 to about 45% by wt, and more preferablyfrom about 20 to about 35% by wt., of the polymer chain. Interpolymersof polyene(s) and vinyl aromatic(s) constitute another preferred type ofelastomer. Especially when such interpolymers are to be used inapplications such as tire treads, the resulting interpolymers preferablyare random in nature, i.e., the mer units derived from each type ofconstituent monomer preferably do not form blocks and, instead, areincorporated in a non-repeating, essentially simultaneous, generallyrandom manner.

Particularly preferred elastomers include poly(butadiene),(poly)isoprene (either natural or synthesized), and interpolymers ofbutadiene and styrene such as, e.g., copoly(styrene/butadiene) alsoknown as SBR.

Polyenes can incorporate into polymeric chains in more than one way.Especially for tire tread applications, controlling the manner in whichthe polyene mer units are incorporated into the polymer (i.e., the1,2-microstructure of the polymer) can be desirable. Based on totalpolyene content, a polymer chain preferably has an overall1,2-microstructure of from about 10 to about 80%, more preferably offrom about 25 to 65%.

The number average molecular weight (M_(n)) of the polymer preferably issuch that a quenched sample exhibits a gum Mooney viscosity (ML₄/100°C.) of from about 2 to about 150.

The foregoing polymers can be made by emulsion polymerization orsolution polymerization, with the latter affording greater control withrespect to such properties as randomness, microstructure, etc. Solutionpolymerizations have been performed since about the mid-20th century,and the general aspects thereof are known to the ordinarily skilledartisan, although certain aspects are provided here for convenience ofreference.

Solution polymerization typically involves an initiator. Exemplaryinitiators include organolithium compounds, particularly alkyllithiumcompounds. Preferred organolithium initiators includeN-lithio-hexamethyleneimine; n-butyllithium; tributyltin lithium;dialkylaminolithium compounds such as dimethylaminolithium,diethylamino-lithium, dipropylaminolithium, dibutylaminolithium and thelike; dialkylaminoalkyl-lithium compounds such asdiethylaminopropyllithium; and those triaUkly stanyl lithium compoundsinvolving Ci—C₁₂ preferably Ci—C₄, alkyl groups.

Multifunctional initiators, i.e., initiators capable of forming polymerswith more than one living end, also can be used. Examples ofmultifunctional initiators include, but are not limited to,1,4-dilithiobutane, 1,10-dilithiodecane, 1,20-dilithioeicosane,1,4-dilithiobenzene, 1,4-dilithionaphthalene, 1,10-dilithioanthracene,1,2-dilithio-1,2-diphenylethane, 1,3,5-trilithiopentane,1,5,15-trilithioeicosane, 1,3,5-trilithiocyclohexane,1,3,5,8-tetralithiodecane, 1,5,10,20-tetralithioeicosane,1,2,4,6-tetralittiiocyclohexane, and 4,4′-dilithiobiphenyl.

In addition to the organolithium initiators, also useful are theso-called functionalized initiators that become incorporated into thepolymer chain, thus providing a functional group at the initiated end ofthe chain. Examples of such materials include the reaction product oforganolithium compounds and, for example, N-containing organic compounds(e.g., substituted aldimines, ketimines, secondary amines,^ optionallypre-reacted with a compound such as düsopropenyl benzene. A moredetailed description of these materials can be found in, e.g., U.S. Pat.Nos. 5,153,159 and 5,567,815.

Typical solution polymerization solvents include various C₅-C₁₂ cyclicand acyclic alkanes as well as their alkylated derivatives, certainliquid aromatic compounds, and mixtures thereof. Solvents capable ofquenching the polymerization are avoided.

As mentioned previously, the mer units of the polymer can beincorporated randomly. hi solution polymerizations, randomization aswell as vinyl content (i.e., 1,2-microstracture) can be increasedthrough use of a coordinator, usually a polar compound, in thepolymerization ingredients. Up to 90 or more equivalents of coordinatorcan be used per equivalent of initiator, with the amount depending on,e.g., the amount of vinyl content desired, the level of non-polyenemonomer employed, the reaction temperature, and the nature of thespecific coordinator employed. Compounds useful as coordinators includeorganic compounds having an O or N heteroatom and a non-bonded pair ofelectrons. Examples include dialkyl ethers of mono- and oligo-alkyleneglycols; crown ethers; tertiary amines such as tetramethylethylenediamine; THF; THF oligomers; linear and cyclic oligomeric oxolanylalkanes such as 2,2′-di(tetrahydrofiiryl) propane, di-piperi-dyl ethane,hexamethylphosphoramide, N,N′-dimethylpiperazine, diazabicyclooctane,diethyl ether, tributylamine, and the like. Details of linear and cyclicoligomeric oxolanyl coordinators can be found in U.S. Pat. No.4,429,091, the teaching of which relating to the manufacture and use ofsuch materials is incorporated by reference herein.

Although the ordinarily skilled artisan understands the type ofconditions typically employed in solution polymerization, arepresentative description is provided for the convenience of thereader. The following is based on a batch process, although extendingthis description to, e.g., semi-batch or continuous processes is withinthe capability of the ordinarily skilled artisan.

Polymerization typically begins by charging a blend of the monomer(s)and solvent to a reaction vessel, followed by addition of coordinator(if used) and initiator, which often are added as part of a solution orblend; alternatively, the monomer(s) and coordinator can be added to theinitiator. The procedure typically is carried out under anhydrous,anaerobic conditions. The reactants can be heated to a temperature of upto about 150° C. and agitated. After a desired degree of conversion hasbeen reached, the heat source (if used) can be removed. If the reactionvessel is to be reserved solely for polymerizations, the reactionmixture can be removed to a post-polymerization vessel forfunctionalization and/or quenching.

To make a functionalized polymer, the polymer is provided with afunctional group prior to its quenching. hi the present invention, thisfunctionalization is preceded by the introduction of what has beenreferred to herein as an intermediate unit.

Many classes of compounds can be used to provide the intermediate unit.Each provides a terminal moiety which, in its anionic form, is lessbasic than a secondary amino radical ion. Secondary amino radical ionsare themselves less basic than carbanions; however, both secondary aminoradical ions and carbanions are sufficiently basic that they areterminated by active hydrogens, such as are in amine-containingcompounds.

Examples of ions that are less basic than secondary amino radical ionsinclude, but certainly are not limited to, —O⁻ and —S⁻. This isconvenient because compounds mat contain O and S are plentiful, thusproviding the ordinarily skilled artisan with a wide range of usefulmaterials from which to choose.

A convenient method of delivering this type of terminal moiety to apolymer chain involves introducing a heteroatom-containing cycliccompound into a system that contains a living polymer. The conditionsused to provide the living polymer typically are adequate to open thering of the cyclic structure and allow the resulting radical to attachto the polymer. This radical, which constitutes the intermediate unit,has a terminal moiety which, in its anionic form, is less basic than asecondary amino radical ion.

Examples of heteroatom-containing cyclic compounds include, but are notlimited to, cyclic siloxanes, epoxides, and the S-containing analogs ofeach. Of the siloxanes, preferred are those that can deliver up to 6,preferably 3 to 4, repeating polysiloxane units. Also preferred arethose where at least some, preferably all, of the Si atoms aresubstituted with a C₁-C₆ substituent, preferably a C₁-C₃ alkyl group.Particularly preferred due to availability and cost arehexamethylcyclotrisiloxane and octamethylcyclotetrasiloxane.

With respect to the epoxides and episulfides, a wide range ofcommercially available materials can be utilized. Examples of suchmaterials include various alkylene oxides and sulfides such as butyleneoxide, various cycloalkene oxides and sulfides such as cyclohexeneoxide, 1,2-epoxybutane, ethylene oxide, and3-glycidoxypropyltrimeth-oxysilane; preferred are those materials withboiling points that are sufficiently high so as to remain liquid attemperatures commonly encountered during solution polymerizations. Theintermediate unit resulting from the use of the epoxide or episulfidecan be aliphatic or cyclic. This type of material can result inintermediate units that connect to the polymer chains by acarbon-to-carbon bond.

No particularly unusual reaction conditions or sequences are believed tobe necessary to attach such intermediate units, although exemplaryreaction conditions can be found below in the examples; reactiontemperatures for this attachment generally range from about 45° to about80° C., preferably between about 50° and about 72° C.

Generally, the compound(s) used to provide the intermediate unit is/areadded in amounts so as to provide, on average, no more than twointermediate units per living polymer and preferably no more than oneintermediate unit per living polymer. If more than one intermediate unitinserts itself, a mid-synthesis change in initiator system might becomenecessary. Conversely, by downwardly adjusting the amount ofintermediate-forming compounds used, multiple polymer chains can attachto the same intermediate unit. In one embodiment, the amount ofcompound(s) used to provide the intermediate unit is selected such thatthe molar ratio of intermediate units to functional groups is from about1:1 to about 1:6; in another embodiment, this ratio is about 1:3.

The intermediate unit generally constitutes a relatively minorproportion of the overall macromolecule; in general, its molecularweight typically is no more than about 400 g/mol, preferably no morethan about 360 g/mol, more preferably no more than about 340 g/mol, andmost preferably no more than about 320 g/mol.

As mentioned above, the terminal moiety of the resulting intermediateunit, in its anionic form, is less basic than a secondary amino radicalion. This allows the resulting anion to react with a compound thatincludes a reactive group and functional moiety capable of reacting orinteracting (e.g., bonding, associating, etc.) with particulate fillerssuch as carbon black. Examples of such moieties areheteroatom-containing groups that have an active hydrogen atom attachedto the heteroatom which, otherwise, would tend to terminate living(extended) polymers.

The intermediate-modified living polymer can be reacted with a compoundof the type just described so as to provide the functionalized polymer.Examples of such compounds include, but are not limited to,

-   -   alkoxysilanes such as methyltrimethoxysilane,        tetraethylorthosilicate, 3-amino-propyltriethoxysilane,        N-(3-triemoxy-silylpropyl)-4,5-dihydroimidazole (TEOSI),        3-isocyanatopropyltriethoxysilane,        n-methylaminopropylmethyldimethoxysilane,        n-methylaminopropyltrimethoxysilane,        3-aminopropyltrimethoxysilane, and C₁ ₅ H₃₃NSiOs (available as        S340 from Sigma-Aldrich Co.; St. Louis, Mo.);    -   halogen-containing compounds such as SiCl₄, SnCl₄, acetyl        chloride, p-toluoyl chloride, CHsS(O)₂Cl, p-toluoyl sulfonyl        chloride, 3-chloropropylamine, 3-(2-bromo-ethyl)indole,        n-methyl-3-bromopropylamine,        1-(3-bromopropyl)-2,2,5,5-tetramethyl-1-aza-2,5-disilacyclo        ρentane, (CH₃)₂SiCl₂, and (CH₃)₃SiCl;    -   anhydrides such as acetic anhydride, 4-methylbenzoic acid        anhydride, methyl succinic anhydride, 4-methylphenyl-succmic        anhydride, and 2-dodecen-1-yl succinic anhydride;    -   nitrogen-containing compounds such as formamide, DMF,        2-cyanopyrimidine, 1,3-propanediamine, and        1,4-diaminocyclohexane;    -   and O- and S-containing compounds such as sultones (e.g.,        1,4-butane sultone).

Quenching typically is conducted by stirring the polymer and an activehydrogen-containing compound (e.g., an alcohol) for up to about 120minutes at temperatures of from about 30° C. to 150° C. Solvent can beremoved by conventional techniques such as drum drying, extruder drying,vacuum drying or the like, which may be combined with coagulation withwater, alcohol or steam, thermal desolvation, etc.; if coagulation isperformed, oven drying may be desirable.

The functionalized polymer can be utilized in a tread stock compound orcan be blended with any conventionally employed tread stock rubber whichincludes natural rubber and/or non-functionalized synthetic rubbers suchas, e.g., one or more of poly(isoprene), SBR, poly(butadiene), butylrubber, neoprene, ethylene/propylene rubber (EPR),ethylene/propylene/diene rubber (EPDM), acrylonitrile/butadiene rubber(NBR), silicone rubber, fluoroelastomers, ethylene/acrylic rubber,ethylene/vinyl acetate inter-polymer (EVA), epichlorohydrin rubbers,chlorinated polyethylene rubbers, chlorosulfonated polyethylene rubbers,hydrogenated nitrile rubber, tetrafluoroethylene/propylene rubber andthe like. When a functionalized polymer(s) is blended with conventionalrubber(s), the amounts can vary from about 5 to about 99% by wt. of thetotal rubber, with the conventional rubber(s) making up the balance ofthe total rubber. The minimum amount depends largely on the degree ofreduced hysteresis desired.

Amorphous silica (SiO₂) can be utilized as a filler. Silicas aregenerally classified as wet-process, hydrated silicas because they areproduced by a chemical reaction in water, from which they areprecipitated as ultrafine, spherical particles. These primary particlesstrongly associate into aggregates, which in turn combine less stronglyinto agglomerates. “Highly dispersible silica” is any silica having avery substantial ability to de-agglomerate and to disperse in anelastomeric matrix, which can be observed by thin section microscopy.

Surface area gives a reliable measure of the reinforcing character ofdifferent silicas; the Brunauer, Emmet and Teller (“BET”) method(described in J. Am. Chem. Soc, vol. 60, p. 309 et seq.) is a recognizedmethod for determining surface area. BET surface areas of less than 450m²/g, from about 32 to about 400 m²/g, from about 100 to about 250 m²/g,and from about 150 to about 220 m²/g are preferred.

The pH of the silica filler is generally from about 5 to about 7 orslightly over, preferably from about 5.5 to about 6.8.

Some commercially available silicas which may be used include Hi-Sil™215, Hi-Sil™ 233, and Hi-Sil™ 190 (PPG Industries, Inc.; Pittsburgh,Pa.). Other suppliers of commercially available silica include DegussaCorp. (Parsippany, N.J.), Rhodia Silica Systems (Cranbury, N.J.), andJ.M. Huber Corp. (Edison, N.J.).

Silica can be employed in an amount of from about 1 to about 100 partsby weight (pbw) per 100 parts of polymer (phr), preferably from about 5to about 80 phr. The useful upper range is limited by the high viscositytypically imparted by fillers of this type.

Other useful fillers include all forms of carbon black including, butnot limited to, furnace black, channel blacks and lamp blacks. Morespecifically, examples of the carbon blacks include super abrasionfurnace blacks, high abrasion furnace blacks, fast extrusion furnaceblacks, fine furnace blacks, intermediate super abrasion furnace blacks,semi-reinforcing furnace blacks, medium processing channel blacks, hardprocessing channel blacks, conducting channel blacks, and acetyleneblacks; mixtures of two or more of these can be used. Carbon blackshaving a surface area (EMSA) of at least 20 m²/g, preferably at leastabout 35 to about 200 m²/g or higher are preferred; surface area valuescan be determined by ASTM D-1765 using the ceryltrimethyl-ammoniumbromide (CTAB) technique. The carbon blacks may be in pelletized form oran unpelletized flocculent mass, although unpelletized carbon black canbe preferred for use in certain mixers.

The amount of carbon black can be up to about 50 phr, with about 5 toabout 40 phr being typical. When carbon black is used with silica, theamount of silica can be decreased to as low as about 1 phr; as theamount of silica decreases, lower amounts of the processing aids, plussilane if any, can be employed.

Elastomeric compounds typically are filled to a volume fraction, whichis the total volume of filler(s) added divided by the total volume ofthe elastomeric stock, of about 25%; accordingly, typical (combined)amounts of reinforcing fillers, i.e., silica and carbon black, is about30 to 100 phr. In certain preferred embodiments, compositions thatinclude the functionalized polymer of the present invention can includecarbon black as the primary filler (i.e., a majority of the filler iscarbon black) or the only filler.

When silica is employed as a reinforcing filler, addition of a couplingagent such as a silane is customary so as to ensure good mixing in, andinteraction with, the elastomer(s). Generally, the amount of silane thatis added ranges between about 4 and 20% by weight, based upon the weightof silica filler present in the elastomeric compound.

Coupling agents can have a general formula of Z-T—X, in which Zrepresents a functional group capable of bonding physically and/orchemically with a group on the surface of the silica filler (e.g.,surface silanol groups); T represents a hydrocarbon group linkage; and Xrepresents a functional group capable of bonding with the elastomer(e.g., via a S-containing linkage). Such coupling agents includeorganosilanes, in particular polysulfurized alkoxysilanes (see, e.g.,U.S. Pat. Nos. 3,873,489, 3,978,103, 3,997,581, 4,002,594, 5,580,919,5,583,245, 5,663,396, 5,684,171, 5,684,172, 5,696,197, etc.) orpolyorganosiloxanes bearing the X and Z functionalities mentioned above.One preferred coupling agent isbis[3-(triethoxysilyl)propyl]tetrasulfide.

Addition of a processing aid can be used to reduce the amount of silaneemployed. See, e.g., U.S. Pat. No. 6,525,118 for a description of fattyacid esters of sugars used as processing aids. Additional fillers usefulas processing aids include, but are not limited to, mineral fillers,such as clay (hydrous aluminum silicate), talc (hydrous magnesiumsilicate), and mica as well as non-mineral fillers such as urea andsodium sulfate. Preferred micas contain principally alumina, silica andpotash, although other variants are also useful, as set forth below. Theadditional fillers can be utilized in an amount of up to about 40 phr,preferably up to about 20 phr.

Other conventional rubber additives also can be added. These include,for example, plasticizers, antioxidants, curing agents and the like.

All of the ingredients can be mixed using standard equipment such as,e.g., Banbury or Brabender mixers.

Reinforced rubber compounds conventionally are cured with about 0.2 toabout 5 phr of one or more known vulcanizing agents such as, forexample, sulfur or peroxide-based curing systems. A general overview ofsuitable vulcanizing agents can be found in any of a variety oftreatises such as, e.g., Kirk-Othmer, Encyclopedia of Chem. Tech., 3ded, (Wiley Interscience, New York, 1982), vol. 20, pp. 365-468.

The following non-limiting, illustrative examples provide the readerwith detailed conditions and materials that can be useful in thepractice of the present invention.

EXAMPLES

For all examples, dried glass vessels previously sealed with extractedseptum liners and perforated crown caps under a positive N₂ purge,butadiene (−21% by wt. in hexane), styrene (33% by wt. in hexane),hexane, n-butyllithium (1.7 M in hexane), oligomeric oxolanyl propanes(1.6 M solution in hexane, stored over CaH₂), and BHT solution in hexanewere used.

Commercially available reagents and starting materials included thefollowing, all of which were used without further purification unlessotherwise noted:

-   -   from ACROS Organics (Geel, Belgium): methyltrimethoxysilane,        tetraethyl orthosilicate, 3-aminopropyltriethoxysilane,        hexamethylcyclotrisiloxane, and octa-methylcyclotetrasiloxane        (with the cyclic siloxanes being dried over CaH₂ prior to use);    -   from Sigma-Aldrich Co.: SiCl₄ and SnCl₄    -   from Gelest, Inc. (Morrisville, Pa.): TEOSI,        3-isocyanatopropyl-triethoxysilane,        N-methylaminopropyhnethyldimethoxysilane, and        N-methylamino-propyltrimethoxysilane.

Testing data in the Examples was performed on filled compositions madeaccording to the formulations shown in Tables Ia and Ib. In these,N-phenyl-iV′-(1₅3-dimethylburyl)-p-phenyldiamine acts as an antioxidantwhile benzothiazyl-2-cyclohexyl-sulfenamide, JV.JV′-diphenyl guanidine,and di(phenylthio)acetamide act as accelerators.

TABLE Ia Compound formulation, carbon black only Amount fphf)Masterbatch polymer 100 carbon black (N343 type) 55 wax 1N-phenyl-N′-(1,3-dimethylbutyl)-p-phenyldiamine 0.95 ZnO 2.5 stearicacid 2 aromatic processing oil 10 Final sulfur 1.3benzothiazyl-2-cyclohexylsulfenamide 1.7 JV,iV′-diphenyl guanidine 0.2TOTAL 174.65

TABLE Ib Compound formulation, carbon black and silica Amount (phr)Masterbatch polymer 100 silica 30 carbon black (N343 type) 35N-phenyl-N′-(1,3-dimethylbutyl)-p-phenyldiamine 0.95 stearic acid 1.5aromatic processing oil 10 Re-mill 60% disulfide silane on carrier 4.57Final ZnO 2.5 sulfur 1.7 benzothiazyl-2-cyclohexylsulfenamide 1.5di(phenylthio)acetamide 0.25 N,N′-diphenyl guanidine 0.2 TOTAL 188.47

Data corresponding to “50° C. Dynastat tan δ” were acquired from testsconducted on a Dynastat™ mechanical spectrometer (DynastaticsInstruments Corp.; Albany, N.Y.) using the following conditions: 1 Hz, 2kg static mass and 1.25 kg dynamic load, a cylindrical (9.5 mmdiameter×16 mm height) vulcanized rubber sample, and 50° C.

Data corresponding to “Bound Rubber” were determined using the proceduredescribed by J J. Brennan et al., Rubber Chem. and Tech., 40, 817(1967).

Examples 1-3 Standard Initiator (n-BuLi)

For Examples 1-3, a polymer batch was prepared using a standardorganolithium initiator. Three samples were taken and reacted withdifferent compounds.

To a N₂-purged reactor equipped with a stirrer was added 1.47 kg hexane,0.41 kg styrene (in hexane), and 2.60 kg butadiene (in hexane). Thereactor was charged with 3.68 mL n-butyllithium solution followed by1.18 mL OOPs solution. The reactorjacket was heated to 50° C. and, after−22 minutes, the batch temperature peaked at ˜66° C. After an additional10 minutes, the polymer cement was removed from the reactor and storedin separate dried glass vessels.

The vessels were placed in a 50° C. bath for 30 minutes. To two of thevessels (samples 1 and 2) were added, respectively,N,N-TMS-aminopropyltriethoxysilane and hexamethylcyclotrisiloxane (1.0 Min hexane); to the other was added isopropanol as a quenching agent.Each was coagulated in isopropanol containing BHT and drum dried.

Examples 4-5 Functional Initiator (DAPDT)

For Examples 4-5, a polymer batch was prepared using a functionalinitiator. Two samples taken from this batch were terminated separately.

To aNrpurged reactor equipped with a stirrer was added 1.47 kg hexane,0.41 kg styrene, and 2.60 kg butadiene (in hexane). The reactor wascharged with a mixture of 1.48 g 2-(4-dirnethylamino)phenyl-1,3-ditbianein 10 nL THF, 1 mL triethylamine, and 3.68 mL n-butyllithrum solution.The contents were agitated at 24° C. for 5 minutes before addition of1.04 mL OOPs solution. The reactor jacket was heated to 50° C. and,after ˜18 minutes, the batch temperature peaked at ˜71° C. After anadditional 10 minutes, samples of the polymer cement were removed fromthe reactor and stored in separate dried glass vessels.

Further processing was performed in a 50° C. bath for 30 minutes; sample4 was reacted with hexamethylcyclotrisiloxane (1.0 M in hexane) whilesample 5 was quenched with isopropanol. Each was coagulated and drumdried as described above with respect to Examples 1-3.

The samples prepared in Examples 1-5 were used to prepare to preparevulcanizable elastomeric compounds containing reinforcing fillers usingthe formulation from Table Ib.

Results of physical testing on these compounds are shown below in Table2. From this data, a reinforced SBR polymer having ahexamethylcyclotrisiloxane-derived intermediate unit (Examples 2 and 4),regardless of the type of initiator used, can be seen to provide agreater than 30% reduction in tan δ (see 50° C. strain sweep data)compared to a control polymer (Examples 3 and 5, respectively). ATMS-protected aminopropyltri-ethoxysilane-reacted polymer (Example 1)showed a slight reduction in tan δ compared to its base polymer (Example3).

TABLE 2 Testing data from Examples 1-5 1 2 3 4 5 M_(n) (kg/mol) 104 102102 120 115 Mw/M_(n) 1.17 1.03 1.04 1.08 1.04 % coupling 8.2 0.0 0.0 7.28.9 T₈ (° C.) −36.4 −37.1 −36.0 −38.4 −38.0 171° C. MDR t50 (min) 7.26.6 6.3 5.8 5.21 171° C. MH-ML (kg-cm) 20.8 15.4 22.8 17.5 24.51 ML₁₊₄ @130° C. 53.3 78.8 49.9 ND¹ 70.0 300% modulus @ 23° C. (MPa) 8.3 11.5 8.112.9 10.5 Tensile strength @ 23° C. (MPa) 12.6 15.3 11.2 18.3 14.8 Temp,sweep 0° C. tan δ 0.181 0.228 0.177 0.229 0.182 Temp, sweep 50° C. tan δ0.234 0.203 0.241 0.162 0.211 RDA 0.25-14% ΔG′ (MPa) 7.359 0.209 7.8721.932 6.235 50° C. RDA strain sweep (5% strain) tan δ 0.2352 0.17250.2606 0.1398 0.2068 50° C. Dynastat tan δ 0.2105 0.1656 0.2111 0.13940.1864 ¹Not determined. Initial surge in property exceeded pre-set limitfox testing device.

Examples 6-24 Functionalized Polymers with HexamethylcyclotrisiloxaneIntermediate Units

Using essentially the same procedure described for Examples 1-5, aN₂-purged reactor equipped with a stirrer was charged with hexane,styrene, and butadiene, followed by sequential charges of small amountsof n-BuLi and OOPs. The reactor jacket was heated and, after 20-30minutes, the batch temperature peaked at 10°-15° C. above the jackettemperature. After an additional −10 minutes, samples of the polymercement were removed from the reactor and stored in separate dried glassvessels.

In a 50° C. bath for −30 minutes, samples 6, 12, and 18 were quenchedwith isopropanol while the others (7-11, 13-17, and 19-23) were reactedwith hexamethylcyclotrisiloxane to provide an intermediate unit. Threeof these (7, 13, and 19) were quenched with isopropanol while the otherswere reacted with the following materials, followed by isopropanolquenching:

-   -   8) methyltrimethoxysilane,    -   9, 20) 3-aminopropyltriethoxysilane,    -   10) TEOSI,    -   11) S340,    -   14, 21) 3-aminopropyltrimethoxysilane,    -   15, 23) [3-(methylamino)propyl]trimethoxysilane,    -   16) 2-dodecen-1-yl succinic anhydride,    -   17)        1-(3-bromopropyl)-2₅2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane,    -   22) N-[3-(trimethoxysilyl)propyl]etkylenediamine, and    -   24) benzosulfimide (i.e., saccharin).

Each sample was coagulated, drum dried, and. compounded substantially asin Examples 1-5 to yield polymers and vulcanizable compositions withproperties as shown below in Table 3 (Examples 6-11), Table 4 (Examples12-17), and Table 5 (Examples 18-24). For those rows that include twodata points, the upper is for a formulation from Table Ia, and the loweris for a formulation from Table Ib.

TABLE 3 Testing/data from Examples 6-11 6 7 8 9 10 11 M_(n) (kg/mol) 9895 100 108 105 105 M_(w)/M_(n) 1.05 1.02 1.08 1.16 1.14 1.13 % coupling4.8 0.0 10.2 21.2 15.5 15.5 Tg (° C.) −35.9 −38.1 −37.7 −37.4 −38.1−37.5 Bound rubber (%) — 7.7 11.7 24.4 19.9 22.7 67.5 66.0 68.1 63.067.3 171° C. MDRt50 (min) — 2.87 3.20 2.49 2.79 2.65 7.19 6.83 7.01 8.436.62 171° C. MH-ML (kg-cm) — 17.1 15.5 15.4 16.4 17.8 16.0 16.8 15.414.9 15.9 MLi₊₄ @ 130° C. — 16.6 19.9 23.4 23.4 23.3 74.6 72.5 72.3 70.473.8 300% modulus @ 23° C. (MPa) — 10.2 8.9 10.4 10.2 12.0 11.7 12.511.8 10.2 11.8 Tensile strength @ 23° C. (MPa) — 16.1 16.2 18.3 14.417.3 15.3 14.0 16.2 17.1 14.8 Temp, sweep 0° C. tan δ — 0.334 0.3420.335 0.337 0.353 0.244 0.252 0.238 0.236 0.238 Temp, sweep 50° C. tan δ— 0.263 0.265 0.250 0.250 0.244 0.182 0.193 0.187 0.195 0.190 RDA0.25-14% ΔG′ (MPa) — 4.968 4.869 2.941 3.210 4.289 2.113 2.196 1.8221.903 1.974 50° C. RDA strain sweep (5% strain) tan δ — 0.2684 0.28200.2273 0.2353 0.2365 0.1883 0.1786 0.1779 0.1873 0.1790 50° C.Dynastattan δ — 0.2581 0.2635 0.2069 0.2150 0.2055 0.1762 0.1725 0.17630.1771 0.1751

TABLE 4 Testing data from Examples 12-17 12 13 14 15 16 17 M_(n)(kg/mol) 97 99 92 95 103 100 M_(w)/M_(n) 1.03 1.05 1.10 1.08 1.08 1.06 %coupling 0.0 5.0 8.7 8.9 11.5 6.8 T_(g) (° C.) −36.9 −36.8 −36.1 −37.0−37.2 −36.4 Bound rubber (%) 10.7 12.5 32.9 24.1 14.2 11.5 15.9 63.871.1 73.2 19.5 13.9 171° C. MDR t₅₀ (min) 2.96 2.90 2.81 2.74 2.53 3.007.67 7.24 7.04 6.47 6.09 7.37 171° C. MH-ML (kg-cm) 16.7 17.9 15.5 16.816.7 17.5 23.0 16.0 16.4 15.3 16.6 16.5 ML₁₊₄ @ 130° C. 19.9 21.0 27.825.0 23.7 21.3 56.3 81.9 90.0 91.6 80.2 80.2 300% modulus @ 23° C. (MPa)10.3 11.2 11.5 11.0 9.9 10.8 9.9 14.6 16.5 14.4 14.7 14.6 Tensilestrength @ 23° C. (MPa) 17.1 18.0 17.9 17.7 16.1 16.5 12.6 14.5 16.314.5 15.6 16.3 Temp, sweep 0° C. tan δ 0.201 0.199 0.205 0.200 0.1960.202 0.165 0.235 0.242 0.235 0.234 0.240 Temp, sweep 50° C. tan δ 0.2740.273 0.258 0.268 0.271 0.271 0.225 0.190 0.174 0.182 0.196 0.185 RDA0.25-14% ΔG′ (MPa) 4.959 4.816 2.397 3.721 4.540 4.601 9.461 2.629 2.6282.793 2.812 2.570 50° C. RDA strain sweep (5% strain) tan δ 0.28620.2685 0.2136 0.2372 0.2574 0.2583 0.2472 0.1855 0.1825 0.1827 0.16770.1697 50° C. Dynastattan δ 0.2644 0.2457 0.2035 0.2193 0.2559 0.23900.2224 0.1816 0.1726 0.1733 0.1718 0.1628

TABLE 5 Testing data from Examples 18-24 18 19 20 21 22 23 24 Mπ(kg/mol)107 101 102 104 92 103 98 Mw/M_(n) 1.06 1.06 1.16 1.27 1.10 1.08 1.05 %coupling 0 0 6.53 8.22 4.26 0 0 T_(g) (° C.) −35.6 −37.2 −37.1 −37.1−37.0 −37.1 −37.0 Bound rubber (%) 11.5 — 29.3 30.2 28.8 25.9 11.7 18.280.1 82.8 83.9 82.9 76.8 171° C. MDRts0 (min) 2.80 — 2.62 2.54 2.49 2.413.11 7.38 6.92 6.67 5.53 5.85 6.96 171° C. MH-ML (kg-cm) 18.0 — 16.916.1 15.9 17.6 17.1 23.2 14.6 14.8 15.3 15.4 14.8 MLi₊₄ @ 130° C. 26.8 —30.0 30.3 29.0 29.0 23.2 66.7 97.1 97.6 99.5 98.5 72.5 300% modulus @23° C. (MPa) 10.8 — 11.2 10.9 10.4 12.0 10.3 9.6 13.6 13.3 14.7 13.112.0 Tensile strength @ 23° C. (MPa) 17.1 — 16.3 17.7 17.9 19.1 17.313.8 18.0 17.2 15.8 16.5 17.4 Temp, sweep 0° C. tan δ 0.214 — 0.2150.220 0.203 0.208 0.192 0.200 0.258= 0.268 0.262 0.263 0.267 Temp, sweep50° C. tan δ 0.262 — 0.249 0.253 0.249 0.247 0.275 0.232 0.191 0.1830.186 0.184 0.197 RDA 0.25-14% ΔG′ (MPa) 5.187 — 2.179 2.579 2.361 3.0615.324 8.992 2.174 2.051 2.106 2.110 2.564 50° C. RDA strain sweep (5%strain) tan δ 0.2471 — 0.1897 0.2083 0.2068 0.2144 0.2723 0.2267 0.16200.1653 0.1595 0.1668 0.1843 50° C. Dynastattan δ 0.2393 — 0.1780 0.19990.1948 0.1941 0.2493 0.2095 0.1651 0.1708 0.1609 0.1673 0.1858

Examples 25-30 Functionalized Polymers with OctamethylcyclotetrasiloxaneIntermediate Units

The procedure described with respect to Examples 6-24 was, insubstantial part, repeated. Sample 25 was quenched with isopropanol,while samples 26-29 involved reacting a BuLi-initiated SBR withoctamethylcyclotetrasiloxane (instead of hexamethyl-trisiloxane as inExamples 6-24).

Sample 26 was quenched with isopropanol while samples 27-29 were reactedwith, respectively, 3-aminopropyltrimethoxysilane,[3-(methylamino)propyl]trimethoxysilane, and 1,4-butane sultone. Sample30 involved reacting a DAPDT-initiated SBR withocta-methylcyclotetrasiloxane followed by reaction with3-aminopropyltriethoxysilane. All functionalized samples were quenchedwith isopropanol.

Each polymer sample was processed and compounded substantially asbefore. Physical properties of the resulting filled compounds are shownbelow in Table 6.

TABLE 6 Testing data from Examples 25-30 25 26 27 28 29 30 Mn (kg/mol)97 97 87 90 97 93 Mw/M_(n) 1.03 1.03 1.23 1.13 1.03 1.15 % coupling 0 011.6 10.6 0 10.7 Tg (° C.) −35.6 −35.0 −35.4 −35.8 −35.4 −36.3 Boundrubber (%) 9.8 10.5 30.3 25.3 11.7 31.3 19.7 76.7 83.8 81.9 78.3 84.8171° C. MDRt50(min) 3.13 3.01 2.67 2.68 3.10 2.54 7.86 7.56 6.92 6.927.15 6.22 171° C. MH-ML (kg-cm) 17.1 18.1 16.3 16.8 17.1 20.2 21.6 14.615.8 24.8 15.5 17.8 MU₄ @ 130° C. 19.6 19.6 26.5 24.6 20.3 33.3 50.583.5 89.6 87.7 83.4 — 300% modulus @ 23° C. (MPa) 10.3 10.8 11.7 10.810.2 13.6 9.5 13.3 — 14.7 14.4 13.6 Tensile strength @ 23° C. (MPa) 14.915.4 16.4 16.0 14.7 17.3 11.9 13.3 14.1 14.1 13.7 17.5 Temp, sweep 0° C.tan δ 0.217 0.204 0.229 0.207 0.213 0.228 0.198 0.268 0.275 0.276 0.2790.245 Temp, sweep 50° C. tan δ 0.271 0.260 0.256 0.268 0.263 0.210 0.2400.188 0.180 0.186 0.190 0.150 RDA 0.25-14% ΔG′ (MPa) 6.000 5.510 2.6513.447 5.104 2.425 8.373 2.179 2.143 2.235 2.293 2.136 50° C. RDA strainsweep (5% strain) tan δ 0.2955 0.2831 0.2307 0.2512 0.2874 0.1735 0.25890.1820 0.1786 0.1705 0.1840 0.1473 50° C. Dynastattan δ 0.2767 0.25950.2057 0.2360 0.2624 0.1602 0.2187 0.1688 0.1616 0.1562 0.1654 0.1358

Examples 31-36 Functionalized Polymers with Cyclohexene OxideIntermediate Units

The procedure described with respect to Examples 6-24 was, insubstantial part, repeated. Sample 31 was quenched with isopropanol,while samples 32-36 involved reacting BuLi-initiated SBR withcyclohexene oxide.

Sample 32 was quenched with isopropanol while samples 33-36 were reactedwith

-   -   33) 3-aminopropyltrimethoxysilane,    -   34) [3-(methylamino)propyl]trimethoxysilane,    -   35) 2-dodecen-1-yl succinic anhydride, and    -   36) 1,4-butane sultone.        (Samples 33-36 were quenched with isopropanol after being        reacted.)

Each polymer sample was processed and compounded substantially asbefore. Physical properties of the resulting filled compounds are shownbelow in Table 7.

TABLE 7 Testing data from Examples 31-36 31 32 33 34 35 36 M_(n)(kg/mol) 89 90 77 82 95 89 Mw/M_(n) 1.04 1.04 1.12 1.07 1.08 1.03 %coupling 0 0 30.2 0 11.7 0 Tg (° C.) −33.6 −33.9 −33.6 −33.6 −33.7 −33.4Bound rubber (%) 9.1 9.5 16.7 15.9 13.1 10.5 18.3 23.0 24.9 24.5 22.921.3 171° C. MDRt₅₀ (min) 3.27 3.25 2.80 2.94 2.88 3.27 8.63 8.12 8.287.60 6.37 8.40 171° C. MH-ML (kg-cm) 15.5 16.5 16.9 16.2 16.9 15.8 20.120.9 20.5 21.4 22.7 20.5 MU₄ @ 130° C. 18.3 18.5 20.0 20.2 21.3 18.247.4 49.7 48.3 47.9 55.0 50.3 300% modulus @ 23° C. (MPa) 9.7 10.7 11.410.9 11.1 10.0 9.5 10.1 9.8 10.2 10.4 9.5 Tensile strength @ 23° C.(MPa) 14.3 15.8 16.5 16.4 17.1 14.6 12.2 12.5 11.2 11.1 12.2 11.5 Temp,sweep 0° C. tan δ 0.224 0.228 0.230 0.224 0.225 0.231 0.198 0.209 0.2020.203 0.213 0.231 Temp, sweep 50° C. tan δ 0.310 0.284 0.281 0.286 0.2810.287 0.247 0.259 0.248 0.241 0.224 0.253 RDA 0.25-14% ΔG′ (MPa) 4.6915.170 4.570 4.656 4.783 4.713 8.827 8.807 8.107 8.312 8.410 8.448 50° C.RDA strain sweep (5% strain) tan δ 0.2918 0.2878 0.2711 0.2780 0.26690.2868 0.2622 0.2568 0.2621 0.2506 0.2331 0.2540 50° C. Dynastattan δ0.2745 0.2698 0.2598 0.2668 0.2568 0.2724 0.1700 0.2385 0.1690 0.17780.1871 0.1563

Examples 37-42 Fundi OnaliΣed Polymers with Cyclohexene SulfideIntermediate Units

The procedure described with respect to Examples 6-24 was, insubstantial part, repeated. Sample 37 was quenched with isopropanolwhile samples 38-42 involved reacting BuLi-initiated SBR withcyclohexene sulfide.

Sample 38 was quenched with isopropanol while samples 39-42 were reactedwith

-   -   39) 3-aminopropyltrimethoxysilane,    -   40) 2-dodecen-1-yl succinic anhydride,    -   41)        1-(3-bromopropyl)-2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane,        and    -   42) 1,4-butane sultone.        (Samples 39-42 were quenched with isopropanol after being        reacted.)

Each polymer sample was processed and compounded substantially asbefore. Physical properties of the resulting filled compounds are shownbelow in Table 8.

TABLE 8 Testing data from Examples 37-42 37 38 39 40 41 42 M_(n)(kg/mol) 96 103 103 100 102 70 M_(w)/M_(n) 1.03 1.10 1.10 1.08 1.10 1.22% coupling 0 15.3 16.4 10.1 14.6 43.5 Tg (° C.) −35.7 −36.1 −36.7 −36.2−35.3 −36.0 Bound rubber (%) 0 18.5 30.4 17.8 20.8 27.8 2.9 10.3 22.423.0 31.9 14.7 171° C. MDR t₅₀ (min) 3.01 2.84 2.63 2.47 2.93 3.14 7.917.26 6.56 6.13 6.27 8.18 171° C. MH-ML (kg-cm) 16.6 16.8 16.2 16.1 16.617.0 20.9 22.7 22.6 22.4 21.9 16.8 MLi₊₄ @ 130° C. 18.9 29.9 31.6 29.529.5 28.9 56.3 66.7 67.5 68.1 69.2 79.4 300% modulus @ 23° C. (MPa) 9.511.4 11.7 11.3 11.8 10.2 9.4 10.9 11.1 10.4 9.8 9.0 Tensile strength @23° C. (MPa) 15.3 15.6 15.7 16.2 15.5 15.5 12.6 14.9 14.2 14.2 13.7 13.9Temp, sweep 0° C. tan δ 0.207 0.218 0.223 0.228 0.219 0.210 0.174 0.1880.193 0.181 0.193 0.191 Temp, sweep 50° C. tan δ 0.278 0.249 0.256 0.2370.234 0.267 0.225 0.219 0.224 0.213 0.219 0.219 RDA 0.25-14% ΔG′ (MPa)5.817 2.543 2.072 2.103 1.539 3.271 8.183 6.667 5.977 6.863 5.333 4.26350° C. RDA strain sweep (5% strain) tan δ 0.2849 0.2182 0.2063 0.20900.1848 0.2441 0.2595 0.2306 0.2122 0.2106 0.2173 0.2215 50° C. Dynastattan δ 0.2695 0.2053 0.2004 0.1993 0.1716 0.2261 0.2338 0.2031 0.20180.2015 0.2021 0.2055

Examples 43-48 Functionalized Polymers with Butylene Oxide IntermediateUnits

The procedure described with respect to Examples 6-24 was, insubstantial part, repeated. Example 43 was quenched with isopropanolwhile samples 44-48 involved reacting BuLi-initiated SBR with butyleneoxide.

Sample 44 was quenched with isopropanol while samples 45-48 were reactedwith

-   -   45) 3-aminopropyltrimethoxysilane,    -   46) [3-(methylamino)propyl]trimethoxysilane,    -   47) 2-dodecen-1-yl succinic anhydride, and    -   48)        1-(3-bromopropyl)-2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane.

Each polymer sample was processed and compounded substantially asbefore. Physical properties of the resulting filled compounds are shownbelow in Table 9.

TABLE 9 Testing data from Examples 43-48 43 44 45 46 47 48 M_(n)(kg/mol) 96 98 91 92 98 99 Mw/M_(n) 1.04 1.03 1.08 1.05 1.03 1.04 %coupling 0 0 6.4 3.2 1.8 3.1 T_(g) (° C.) −36.1 −35.9 −35.5 −36.1 −35.8−35.5 Bound rubber (%) 8.3 9.0 14.5 5.9 7.9 9.4 12.3 14.5 19.5 15.6 15.715.2 171° C. MDRt50(min) 2.88 3.00 2.63 2.59 2.89 2.93 7.02 6.90 6.525.78 6.29 6.94 171° C. MH-ML (kg-cm) 16.6 16.5 16.5 16.6 16.5 16.7 18.419.6 18.9 20.8 19.8 19.3 MU4@ 130° C. 20.0 21.0 22.2 20.8 20.3 20.4 39.240.4 41.2 — 40.9 40.9 300% modulus @ 23° C. (MPa) 10.2 9.9 10.5 10.510.3 10.4 8.5 9.8 10.4 11.5 9.1 9.9 Tensile strength @ 23° C. (MPa) 15.316.2 16.4 15.2 16.7 17.2 11.4 12.7 13.3 13.9 11.3 12.1 Temp, sweep 0° C.tan δ 0.202 0.211 0.202 0.212 0.213 0.212 0.193 0.197 0.201 0.205 0.1930.198 Temp, sweep 50° C. tan δ 0.261 0.274 0.265 0.271 0.261 0.270 0.2570.258 0.263 0.257 0.241 0.252 RDA 0.25-14% ΔG′ (MPa) 5.395 4.820 4.5074.911 4.392 5.190 8.063 7.646 4.198 7.669 6.918 7.670 50° C. RDA strainsweep (5% strain) tan δ 0.2764 0.2818 0.2729 0.2815 0.2730 0.2870 0.26530.2570 0.2357 0.2386 0.2216 0.2458 50° C. Dynastattan δ 0.2572 0.26270.2506 0.2574 0.2538 0.2584 0.2421 0.2322 0.2279 0.2288 0.2211 0.2310

1. A method of providing an amine-functionalized polymer, comprising: a)in a reaction medium comprising at least one of a C₅-C₁₂ cyclic alkane,a C₅-C₁₂ acyclic alkane, an alkylated C₅-C₁₂cyclic alkane, an alkylatedC₅-C₁₂ acyclic alkane, or a liquid aromatic solvent, reacting a polymerthat consists essentially of polyene mer and, optionally, vinyl aromaticmer, said polymer having a living terminus, with a cyclic compoundcomprising three or four siloxane units in its ring structure so as toprovide an intermediate functionalized living polymer having at itsterminus a radical of said cyclic compound, said radical constituting nomore than about 400 g/mol of said intermediate functionalized livingpolymer; and b) introducing into said reaction medium an aminecomprising an active hydrogen atom attached to the amino nitrogen atomof said amine and allowing said amine to chemically bond to saidintermediate functionalized living polymer, thereby providing saidamine-functionalized polymer.
 2. The method of claim 1 wherein at leastone of the silicon atoms of said cyclic compound comprises at least oneC₁-C₆ substituent.
 3. The method of claim 1 wherein each of the siliconatoms of said cyclic compound comprises at least one C₁-C₆ substituent.4. The method of claim 3 wherein said cyclic compound ishexa-methylcyclotrisiloxane or octamethylcyclotetrasiloxane.
 5. Themethod of claim 1 wherein said polymer has an overall 1,2-microstructureof from about 25 to 65%.
 6. The method of claim 1 wherein said reactionmedium further comprises a polar coordinating compound.
 7. The method ofclaim 1 wherein said polymer comprises about 1 to about 50 weightpercent vinyl aromatic mer units.
 8. The method of claim 7 wherein saidvinyl aromatic mer units are randomly distributed in said polymer. 9.The method of claim 8 further comprising removing saidamine-functionalized polymer from said reaction medium and blending saidamine-functionalized polymer with one or more types of filler particlesso as to form a rubber compound.
 10. The method of claim 9 wherein saidrubber compound further comprises at least one other type of rubber. 11.The method of claim 10 wherein said rubber compound further comprises avulcanizing agent.
 12. The method of claim 11 further comprisingvulcanizing said rubber compound.
 13. The method of claim 1 furthercomprising removing said amine-functionalized polymer from said reactionmedium and blending said amine-functionalized polymer with one or moretypes of filler particles so as to form a rubber compound.
 14. Themethod of claim 13 wherein said rubber compound further comprises atleast one other type of rubber.
 15. The method of claim 14 wherein saidrubber compound further comprises a vulcanizing agent.
 16. The method ofclaim 15 further comprising vulcanizing said rubber compound.